See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/216213638

Size-Controlled Synthesis of Magnetite

Nanoparticles in the Presence of Polyelectrolytes
ARTICLE in CHEMISTRY OF MATERIALS SEPTEMBER 2004
Impact Factor: 8.35 DOI: 10.1021/cm049205n

CITATIONS

READS

187

62

6 AUTHORS, INCLUDING:
Satyabrata Si

Tarun Mandal

KIIT University

Indian Association for the Cultivation of Scie

33 PUBLICATIONS 943 CITATIONS

82 PUBLICATIONS 2,425 CITATIONS

SEE PROFILE

SEE PROFILE

Available from: Satyabrata Si

Retrieved on: 28 March 2016

Chem. Mater. 2004, 16, 3489-3496

3489

Size-Controlled Synthesis of Magnetite Nanoparticles in

the Presence of Polyelectrolytes
Satyabrata Si, Atanu Kotal, Tarun K. Mandal,*, Saurav Giri,,
Hiroyuki Nakamura, and Takao Kohara
Polymer Science Unit and Department of Solid State Physics, Indian Association for the
Cultivation of Science, Jadavpur, Kolkata 700 032, India, and Graduate School of Material
Science, University of Hyogo, Kamigori, Ako-gun, Hyogo 678-1297, Japan
Received May 19, 2004

Magnetite nanoparticles of nearly uniform size have been prepared by precipitating ferrous
ions in the presence of two different polyelectrolytes, viz., poly(acrylic acid) and the sodium
salt of carboxymethyl cellulose at high pH (13). The size of the magnetite nanoparticles
can be controlled easily by varying the concentration of the polyelectrolyte in the medium.
Transmission electron microscopy study indicates that the average particle size varies from
5 to 15 nm, depending on the concentration and the nature of the polyelectrolyte. X-ray
diffraction study shows the presence of only magnetite phase. FTIR spectroscopy and
thermogravimetric analysis confirmed the presence of polyelectrolyte on the magnetite
surface. The magnetization and Mossbauer studies were performed on two samples with
mean diameters 7.0 and 14.7 nm. Magnetization measurements suggest that both of these
particles are of single magnetic domain. The measurements also estimate the superparamagnetic blocking temperature, TB ) 145 K for smaller particles, while TB > 300 K for the
larger particles. Mossbauer spectra at 300 K show only a quadrupole doublet for the smaller
particles and mostly a magnetically separated sextet for the larger ones, indicating also the
marked size dependence of moment dynamics.

Introduction
Nowadays shape- and size-controlled synthesis of
magnetic oxide nanoparticles is of great technological
and fundamental scientific importance. Magnetite (Fe3O4)
is one of the phases of iron oxide that finds numerous
applications due to its extraordinary magnetic and
optical properties.1 Magnetite has an inverse spinel
structure where O2- ions are cubic close packed (ccp),
the Fe2+ ions are in octahedral sites, and the Fe3+ ions
are half in octahedral and half in tetrahedral sites.2
Owing to its structure, magnetite is a typical semiconducting material, which is mainly found useful in
various applications such as magnetic storage media,3
printing inks,4 magnetic resonance imaging,5 drug
delivery,6 biomedicine,7 biosensors,8 magnetic refrigera* To whom correspondence should be addressed. Phone: 91-332473-4971. E-mail: psutkm@iacs.res.in.
Polymer Science Unit, Indian Association for the Cultivation of
Science.
Department of Solid State Physics, Indian Association for the
Cultivation of Science.
University of Hyogo.
(1) Yasumori, A.; Matsumoto, H.; Hayashi, S.; Okada, K. J. SolGel Sci. Techn. 2000, 18, 249-258; Mamedov, A.; Ostrander, J.; Aliev,
F.; Kotov, N. A. Langmuir 2000, 16, 3941-3949.
(2) Cornell, R. M.; Schwertmann, U. The Iron Oxides: Structure,
Properties, Reactions, Occurrence and Uses; VCH: New York, 1996.
(3) Yamaguchi, K.; Matsumoto, K.; Fujii, T. J. Appl. Phys. 1990,
67, 4493.
(4) Peikove, V. T.; Jeon, K. S.; Lane, A. M. J. J. Magn. Magn. Mater.
1999, 193, 307.
(5) Oswald, P.; Clement, O.; Chambon, C.; Schouman-Claeys, E.;
Frija, G. Magn. Reson. Imaging 1997, 15, 1025.

tion,9 color imaging,10 bioprocessing,11 high-grade magnetic separation, and ferrofluids.12 Conventional magnetic recording media have been fabricated by incorporating micrometer-sized iron oxide particles along with
polymer/surfactant into a thin film. Recently there has
been considerable interest in magneto-optic devices,
which require magnetic particles of size below 10 nm.
These small particles are optically transparent and ideal
candidates for incorporation into ultrathin films of
polymers.13 Most of these technological and diagnostic
applications also require magnetic particles of size
smaller than 20 nm and a narrow size distribution. The
physical and chemical properties of magnetic nanoparticles strongly depend on their size. Thus, the control
over size and particularly size distribution without
particle aggregation becomes a challenge for the fabrication of nanoscale devices and their use in bioanalytical
applications.
(6) Roullin, V. G.; Deverre, J. R.; Lemaire, L.; Hindre, F.; Julienne,
M. C. V.; Vienet, R.; Benoit, J. P. Eur. J. Pharm. Biopharm. 2002, 53,
293.
(7) Fu, L.; Dravid, V. P.; Jhonson, D. L. Appl. Surf. Sci. 2001, 181,
173.
(8) Perez, J. M.; Simeone, F. J.; Saeki, Y.; Josephson, L.; Weissleder,
R. J. Am. Chem. Soc. 2003, 125, 10192.
(9) McMichael, R. D.; Shull, R. D.; Swartzendruber, L. J.; Bennett,
L. H.; Walson, R. E. J. Magn. Magn. Mater. 1992, 111, 29.
(10) Ziolo, R. F. In U.S. Patent No. 4474866, 1984.
(11) Nixon, L.; Koval, C. A.; Noble, R. D.; Slaff, G. S. Chem. Mater.
1992, 4, 117.
(12) Anton, A. I. J. Magn. Magn. Mater. 1990, 85, 137-140.
(13) Kang, Y. S.; Risbud, S.; Rabolt, J. F.; Stroeve, P. Chem. Mater.
1996, 8, 2209-2211.

10.1021/cm049205n CCC: $27.50 2004 American Chemical Society

Published on Web 07/31/2004

3490

Chem. Mater., Vol. 16, No. 18, 2004

Magnetite is generally prepared mainly by three

processes, viz., (1) coprecipitation of an aqueous solution
of Fe2+/Fe3+ in the presence of a base, usually an alkali
hydroxide or ammonia;14,15 (2) thermal decomposition
of an iron complex using an oxidizing agent;16 and (3)
by a sonochemical approach.17 The particles have a large
surface-area-to-volume ratio, which causes particle aggregation during particle formation through van der
Waals or other force of attraction to reduce their surface
energy. Consequently, several reports have been published on stabilizing these particles using different stabilizers such as a surfactant or a polymer
matrix.16,18-24 Among these reports a considerable
amount of work has been executed where magnetite
particles are first prepared and then stabilized using a
stabilizer.14,20,22,23 Recently, magnetic polystyrene nanoparticles have been prepared by the miniemulsion
technique using presynthesized magnetite stabilized
with oleic acid.22 Lin et al. has reported the preparation
of poly(acrylic acid)-coated Fe3O4 nanoparticles using
this method.23 Their particles show both ferro- and
superparamagnetism. One of the main disadvantages
of this method is that the particle size distribution can
not be controlled, and also it is a time-consuming
process. On the other hand, magnetite particles prepared in the presence of a stabilizer prevent particle
coalescence during formation, resulting in a very small
particle with narrow size distribution and in various
sizes depending upon the experimental parameters.
Therefore, many attempts have been made to synthesize
magnetic nanoparticles in the presence of surfactants16,25 or polymeric compounds with some specific
functional groups as stabilizers.24,26 For example, Sun
et al. has synthesized 3-20 nm Fe3O4 nanoparticles
using seed-mediated growth from a iron complex in
organic phase at high temperature.16 They have tuned
the particle size using smaller particles as seeds.
Superparamagnetic magnetite nanoparticles have also
been prepared by solvothermal reduction in the presence
of ethylene glycol, oleic acid, and trioctyl phosphine
oxide or hexadecylamine.27 Magnetite nanoparticles
have also been successfully synthesized using poly(14) Sahoo, Y.; Pizem, H.; Fried, T.; Golodnitsky, D.; Burstein, L.;
Sukenik, C. N.; Markovich, G. Langmuir 2001, 17, 7907-7911.
(15) Lee, J.; Isobe, T.; Senna, M. J. Colloid Interface Sci. 1996, 177,
490.
(16) Sun, S.; Zeng, H. J. Am. Chem. Soc. 2002, 124, 8204-8505.
(17) Vijayakumar, R.; Koltypin, Y.; Felner, I.; Gedanken, A. Mater.
Sci. Eng. A 2000, 286, 101-105.
(18) Zhou, Z. H.; Wang, J.; Liu, X.; Chan, H. S. O. J. Mater. Chem.
2001, 11, 1704-1709.
(19) Ziolo, R. F.; Giannelis, E. P.; Weinstein, B. A.; OHoro, M. P.;
Ganguly, B. N.; Mehrotra, V.; Russell, M. W.; Huffman, D. R. Science
1992, 257, 219-222; Rabelo, D.; Lima, E. C. D.; Reis, A. C.; Nunes,
W. C.; Novak, M. A.; Garg, V. K.; Oliveira, A. C.; Morais, P. C. Nano
Lett. 2001, 1, 105-108.
(20) Xie, G.; Zhang, Q. Y.; Luo, Z. P.; Wu, M.; Li, T. H. J. Appl.
Polym. Sci. 2003, 87, 1733-1738.
(21) Wang, L. W.; Teng, X.; Wang, J. S.; Yang, H. Nano Lett. 2003,
3, 789.
(22) Ramirez, L. P.; Landfester, K. Macromol. Chem. Phys. 2003,
204, 22-31.
(23) Lin, Y. J.; Wang, L.; Lin, J. G.; Huang, Y. Y.; Chiu, W. Y. Synth.
Met. 2003, 135-136, 769-770.
(24) Lin, H.; Watanabe, Y.; Kimura, M.; Hanabusa, K.; Shirai, H.
J. Appl. Polym. Sci. 2003, 87, 1239-1247.
(25) Fried, T.; Shemer, G.; Markovich, G. Adv. Mater. 2001, 13,
1158.
(26) Lee, D. K.; Kang, Y. S.; Lee, C. S.; Stroeve, P. J. Phys. Chem.
B 2002, 106, 7267-7271; Jones, F.; Colfen, H.; Antonietti, M. Colloid
Polym. Sci. 2000, 278, 491-501.
(27) Hou, Y.; Yu, J.; Gao, S. J. Mater. Chem. 2003, 13, 1983.

Si et al.

(styrene acrylate) copolymer gel or porous sulfonated

divinylbenzene copolymer as templates.19,28 Among
these polymers water-soluble polymeric stabilizers are
very important, because the formed magnetic nanoparticles can be used in biomedical applications, as 98% of
our body constituent is mainly water, besides other
applications. Lee et al. has reported the synthesis of
ultrafine Fe3O4 nanoparticles by coprecipitation of Fe2+/
Fe3+ aqueous solution at high pH using poly(vinyl
alcohol) (PVA) as a stabilizer without mentioning any
particle size variation.15 Although there are several
reports on the synthesis of magnetite nanoparticles
using polymer as a stabilizer, none of them refer to the
preparation of magnetite nanoparticles in the presence
of polyelectrolytes where particle size is controlled as a
variable parameter.
Here we report a simple synthetic approach to prepare nearly monodisperse magnetite nanoparticles. We
started from an aqueous solution of Fe(II) salt at high
pH (13) and room temperature where two different
water-soluble polymers, viz, poly(acrylic acid) (PAA) and
sodium salt of carboxymethyl cellulose (NaCMC), have
been used without any oxidizing/reducing agent. Size
as well as the crystallinity of the magnetite nanoparticles were varied by preparing the particles at different
polyelectrolyte concentration. The superparamagnetic
and ferromagnetic features of magnetite nanoparticles
were observed from the Mossbauer and magnetization
studies, where magnetic properties strongly depend on
the size of the particles.
Experimental Section
Materials. Iron(II) sulfate heptahydrate (FeSO4, 7H2O)
(Merck, India) and sodium hydroxide (NaOH) (Merck, India)
were used as received. Acrylic acid (Aldrich, 99%) was distilled
under reduced pressure. The sodium salt of carboxymethyl
cellulose (NaCMC) (British Drug House, London) was used
without further purification. The viscosity-averaged molecular
weight, and degree of substitution were determined earlier
from this laboratory and were found to be 6.5 104 and 0.13,
respectively.29
Synthesis of Poly(acrylic Acid). PAA was prepared in
water at 70 C by solution polymerization using 15% (w/v)
acrylic acid and 0.1% (w/v) ammonium persulfate (APS) as
initiator with constant nitrogen purging. After polymerization
for 2 h, the polymer was precipitated into acetone and purified
by dissolution in water and again reprecipitated into acetone.
It was then dried at 60 C for 48 h in a vacuum oven. The
molecular weight of PAA was determined by a viscometric
method in which intrinsic viscosity was measured using
dioxane as the solvent at 30 C. The viscosity-averaged
molecular weight (Mv) was calculated using the following
Mark-Houwink relation.

[] ) KMva
The constant (K) 76 10-5dL/g and a ) 0.5 for the solvent
dioxane) in the above equation was obtained from the reference
by Newman et al. where molecular weight was determined by
the osmotic pressure method.30 The molecular weight was
found to be 1.5 105.
(28) Qu, S. C.; Yang, H. B.; Ren, D. W.; Kan, S. H.; Zou, G. T.; Li,
D. M.; Li, M. H. J. Colloid Interface Sci. 1999, 215, 190-192.
(29) Banerjee, P. Eur. Polym. J. 1998, 34, 841-847.
(30) Newman, S.; Krigbaum, W. R.; Laugier, C.; Flory, P. J. J.
Polym. Science 1954, 14, 451.

Size-Controlled Magnetite Nanoparticles

Chem. Mater., Vol. 16, No. 18, 2004 3491

Synthesis of Magnetite Nanoparticles. An aqueous

solution of FeSO47H2O (10 mL, 0.1 M) was added dropwise
to a 10 mL aqueous solution of 2% (w/v) PAA with continuous
stirring. The final concentration of the polymer in the medium
was 1% (w/v). The mixture was stirred for 30 min to complete
the formation of the iron-polymer complex. The pH of the
solution was then increased slowly by adding 0.1 M NaOH
solution. The reaction mixture was subsequently aged for 1 h
with constant stirring. The process was repeated with varying
the concentration of PAA, viz., 0.75%, 0.50%, and 0.25% (w/
v), respectively, for preparing size-variable magnetite nanoparticles. Different size magnetite nanoparticles were also
synthesized by varying the concentration of NaCMC using a
reaction procedure similar to that described above. After the
reaction, excess polyelectrolyte was removed by centrifugation
followed by washing with double distilled water. This purification process was repeated three times. The resultant solid
magnetite materials are then dried in a vacuum oven at 60
C for 24 h. All the experiments were performed from dry
polymer-coated magnetite sample after removing excess unadsorbed polyelectrolytes, except in the case of transmission
electron microscopy (TEM).
Characterization. TEM samples were prepared by putting
a drop of the as-prepared magnetite suspension on a carboncoated copper grid and then dried in air. The dried grid was
then placed under a JEOL JEM-200CX transmission electron
microscope. The images were taken at an acceleration voltage
of 120 kV.
The attachment of the polymer on the magnetite particle
surface was confirmed by Fourier-transform infrared spectroscopy (FTIR). FTIR spectra of the polymer-coated magnetite
nanoparticles were recorded from KBr pellets prepared by
mixing dry, coated nanoparticles with KBr in a Series II
Nicolet Magna-IR 750 spectrometer.
The crystallite phase was identified by recording X-ray
powder diffraction patterns (XRD) of the dry, purified samples
using a Philips PW 1830 diffractometer equipped with a Cu
KR radiation source.
The amount of polyelectrolyte adsorbed on the magnetite
nanoparticles was determined by a thermogravimetric analyzer (TGA) using a Mettler Toledo Star System TGA/
SDTA851e in the presence of N2 gas with a heating rate of 20
C/min.
The Mossbauer spectrum was recorded in a transmission
geometry using a 1 GBq 57Co source in a Rh matrix with a
Wissel velocity drive unit in a constant acceleration mode. The
Mossbauer parameters were estimated with respect to R-Fe.
The magnetization study was performed using a SQUID
magnetometer (Quantum Design MPMS-5).

Results and Discussion

First of all, we would like to discuss the chemistry of
the formation of magnetites. Fe3O4 is generally prepared
via coprecipitation of Fe2+ and Fe3+ ions by a base
following this chemical reaction:31

Fe2+ + 2Fe3+ + 8OH- f Fe3O4 + 4H2O

(1)

According to the results of thermodynamic modeling of

this system, a complete precipitation of Fe3O4 is expected in the pH range 7.5-14, while mainly the molar
ratio of Fe2+ and Fe3+ is 1:2. The mixture of Fe2+/Fe3+
ions with a mole ratio of 1:1 has also been used to
prepare magnetite.32 Magnetite can also be formed by
controlled oxidation of a Fe2+ ion solution according to
the following equations:

3Fe2+ + 4H2O f Fe3O4 + 6H+ + 6H2

(2)

Fe2+ + O2 + OH- f Fe3O4 + H+

(3)

As described above there are two possible methods for

magnetite preparation. First, according to the eq 1, the
formation of magnetite requires both ferrous and ferric
ion. However, in our case, magnetite nanoparticles were
prepared only from Fe2+ ion in the presence of polyelectrolyte in air at high pH. It is well-known that Fe2+ ion
can be oxidized easily by oxygen in the air. As a matter
of fact, the ferrous ions that we have used contain some
ferric ions, and during stirring with the polymer,
presumably some of the ferrous ions are oxidized to
ferric ions by oxygen in the air. The color of the ironpolymer complex changed from light green to yelloworange, indicating oxidation of Fe2+ to Fe3+ under air.
When NaOH was added, the color of the solution
changed from yellow-orange through green to black-red,
indicating the formation of magnetite in the presence
of air, and it was quite stable. To study the effect of
atmospheric oxygen on the formation of magnetite
nanoparticles, we have performed the same reaction in
the presence of nitrogen gas. In this case, the color of
the iron-polymer complex also changed to yelloworange, because our original ferrous sample contains a
small amount of ferric ion, as we mentioned previously.
The yellow-orange color changed to green upon NaOH
addition. However, it was remained green while the
nitrogen flow was maintained through the medium.
When this solution was exposed to air, the color changed
to brown and precipitated immediately. Second, magnetite may also be formed following eqs 2 and 3. The
formation mechanism of magnetite in our case is still
unclear.
Figure 1 shows the transmission electron micrograph
of all the PAA-coated Fe3O4, and Figure 2 shows the
CMC-coated Fe3O4 prepared by varying the polymer
concentration. All the samples show that there is nearly
uniform distribution of particle size with high particle
density. Table 1 shows the variation of particle size with
polyelectrolyte concentration, determined by measuring
the size of at least 100 particles from the respective
TEM picture. It clearly indicates that there is a continuous increase of particle size upon decreasing the concentration of PAA as well as NaCMC. The relative
standard deviation (r)33 values reveal that the magnetite nanoparticles prepared at high polyelectrolyte
concentration are relatively more monodisperse than the
particles prepared at low concentration. The nanoparticles are generally considered to be monodisperse, if
the standard deviation ()34 e 5% relative to the average
size, i.e., the value of r lies within 5 for spherical
particles. Furthermore, CMC-coated Fe3O4 nanoparticles show more monodispersity compared to the magnetite particle prepared with PAA. However, in the case
of PAA, the variation of particle size with increasing
PAA concentration is more prominent than for the
particles prepared by varying NaCMC concentration. In
(31) Kim, D. K.; Mikhaylova, M.; Zhang, Y.; Muhammed, M. Chem.
Mater. 2003, 15, 1617-1627.
(32) Godovsky, D. Y.; Varfolomeev, A. V.; Efremova, G. D.;
Cherepanov, V. M.; Kapustin, G. A.; Volkov, A. V.; Moskvina, M. A.
Adv. Mater. Opt. Electron. 1999, 9, 87.
(33) The relative standard deviation of the size distribution was
calculated from the equation r ) 100 /D, where is the standard
deviation and D is the average diameter of particles.
(34) The standard deviation of the size distribution was calculated
from the equation ) [ni(Di - D)2/(N - 1)]0.5, where ni is the number
of particles having diameter Di. D is the average diameter [)(niDi)/
N], and N is the total number of particles.

3492

Chem. Mater., Vol. 16, No. 18, 2004

Si et al.

Figure 1. TEM pictures of the as-prepared PAA-coated Fe3O4 nanoparticles prepared with various PAA concentrations: (a) 1%,
(b) 0.5%, (c) 0.25% (w/v). (d) Selected portion of the electron diffraction pattern of PAA-Fe3O4 nanocomposite prepared in the
presence of 1% PAA.

Figure 2. TEM pictures of the as-prepared CMC-coated Fe3O4 nanoparticles prepared with various NaCMC concentrations: (a)
1%, (b) 0.5%, and (c) 0.25% (w/v).
Table 1. Average Particle Size of Magnetite
Nanoparticles Prepared by Varying Polyelectrolyte
Concentration
mean
concn, diameter,
polyelectrolyte %, w/v
nm
PAA
NaCMC
PAA
NaCMC
PAA
NaCMC

1.00
0.50
0.25

5.1
10.5
7.0
14.4
14.7
15.5

SD
()

rel
SD
(r)

0.42
8.2
0.06
0.6
0.58
8.3
0.92
6.4
4.20 28.5
1.20
7.7

particle size
from Scherers
equation, nm
4.9
6.6
5.8
16.5
9.5
16.7

the case of NaCMC, magnetite nanoparticles were

obtained with a minimum diameter of 10 nm, while the
size of magnetite nanoparticles obtained using PAA was
up to 5 nm. The electron diffraction (ED) pattern of some
selected portion of magnetite nanoparticles prepared

with 1% PAA in Figure 1d indicates that all the rings

are clear and well-defined, which reveals the nanocrystallinity of rather uniform crystallite size.18 The formation of uniform magnetite nanoparticles can be attributed to the attachment of the polyelectrolyte on the
surface of the particles. The existence of polyelectrolytes
thus prevents the coalescence of particles due to the
repulsive interaction between the same charges on the
polyelectrolytes. Thus, the concentration of the polyelectrolyte plays an important role in the preparation
of uniform and size-controlled nanoparticles. In the case
of higher PAA concentration, magnetite nanoparticles
show a relatively better monodispersity. At lower PAA
concentration, the amount of PAA adsorbed on the
magnetite particle surface is lower, which causes an
increased chance of coalescence between nanoparticles,

Size-Controlled Magnetite Nanoparticles

Figure 3. X-ray diffraction pattern of PAA-Fe3O4 nanocomposites prepared with (a) 1%, (b) 0.75%, (c) 0.5%, (d) 0.25%,
and (e) 0% (w/v) of PAA.

Figure 4. X-ray diffraction pattern of CMC-Fe3O4 nanocomposites prepared with (a) 1%, (b) 0.75%, (c) 0.5%, (d) 0.25%,
and (e) 0% (w/v) of NaCMC.

resulting in a broad distribution of particle size. As

shown in Table 1, the highest value of the r depicted
is for the 0.25% PAA. CMC-coated Fe3O4 nanoparticles
also show similar kind of behavior.
The iron oxide phase was identified from the XRD
pattern, as shown in Figures 3 and 4, with peak
positions at 30.00 (220), 35.5 (311), 43.1 (400), 53.4 (422),
57 (511), and 63 (440), which are consistent with the
standard data for magnetite.15,18 Figures 3 and 4 show
that there is continuous broadening of each peak with

Chem. Mater., Vol. 16, No. 18, 2004 3493

the increase in PAA or NaCMC concentration. The XRD

peak broadening is therefore attributed to the decrease
in the particle size.15 This can be verified quantitatively
using Scherers equation,35 which gives a relationship
between peak broadening in XRD and particle size. The
particle sizes estimated by this equation are given in
Table 1. These values confirm that the peak broadening
in the XRD trace with increasing polyelectrolyte concentration is due to the decrease in particle size,
although there is some deviation in the particle sizes
compared to that measured by TEM (see Table 1), which
is due to the use of two different techniques for the
measurements of the size of the particles.36 From Figure
3, it is clear that the relative XRD peak intensity
decreases with increasing PAA concentration, which
indicates that the relative crystallinity of the magnetite
decreased. The XRD pattern of CMC-coated magnetite
nanoparticles also shows a similar decreasing trend
with increasing NaCMC concentration, as displayed in
Figure 4. Besides magnetite peaks, we did not observe
any other peak in the diffraction pattern for all the
samples.
The attachment of the polymer on the particle surface
was confirmed by FTIR spectroscopy. The characteristic
stretching frequencies of PAA at low pH include O-H
stretching at 3431 cm-1; CdO stretching at 1728 cm-1,
and the C-O stretching at 1100-1200 cm-1. At high
pH, PAA shows peaks at 1562 and 1408 cm-1 due to
carboxylate (COO-) asymmetric and symmetric stretching, respectively.37 There is no absorption peak in the
region of CdO for PAA-magnetite nanocomposites
(Figure 5a,b). However, parts a and b of Figure 5 show
the peaks around 1549 and 1397 cm-1, which are due
to asymmetric and symmetric stretching of the COO-,
respectively, along with a peak at 1114 cm-1 for the
C-O stretching of PAA in the composite. This observation suggested that the PAA chains were anchored on
the magnetite particle surface involving bidentate chelation of carboxylate ion of PAA at high pH. The peak
position for carboxylate asymmetric and symmetric
stretching of neat NaCMC was found to be 1622 and
1421 cm-1, respectively (Figure 5c). Spectra for CMCcoated magnetite particles (Figure 5d,e) reveal bands
at 1592 and 1411 cm-1, corresponding to characteristic
asymmetric and symmetric stretching of carboxylate,
respectively, indicating that CMC chains are also attached in a similar fashion on the magnetite surface.
In both cases, the position of the carboxylate asymmetric
and symmetric stretching frequency is slightly blue
shifted when attached to the magnetite particle surface
compared to the unadsorbed PAA at high pH and
NaCMC. This may be attributed to the decrease in force
constant resulting from the inhibition of conjugation of
COO- when attached to a particle surface. In the
unbound caboxylate ion, the C-O bond has partial
double bond character and hence the force constant is
greater, causing absorption at higher wavenumber.
The attachment of the polyelectrolyte on the magnetite particle surface was further confirmed by TGA. In
(35) Cullity, B. D. In Elements of X-ray Diffractions; AdditionWesley: Reading, MA, 1978; p 102.
(36) Bandyopadhyay, S.; Paul, G. K.; Roy, R.; Sen, S. K.; Sen, S.
Mater. Chem. Phys. 2002, 74, 83-91.
(37) Kirwan, L. J.; Fawell, P. D.; Bronswijk, W. V. Langmuir 2003,
19, 5802.

3494

Chem. Mater., Vol. 16, No. 18, 2004

Si et al.

Figure 7. TGA thermograms of (a) pure NaCMC and CMCFe3O4 nanocomposites prepared by employing (b) 1% NaCMC
and (c) 0.25% NaCMC.

Figure 5. FTIR spectra of (a) Fe3O4 prepared with 0.5% PAA,

(b) Fe3O4 prepared with 1% PAA, (c) pure NaCMC, (d) Fe3O4
prepared with 0.25% NaCMC, and (e) Fe3O4 prepared with 1%
NaCMC.

Figure 6. TGA thermograms of (a) pure PAA and PAA-Fe3O4

nanocomposites prepared by employing (b) 1% PAA and (c)
0.25% PAA.

case of PAA-coated magnetite, TGA thermograms show

a continuous weight loss in the temperature range of
200-550 C, which is the range of decomposition temperature for PAA (compare parts a and b of Figure 6).
Similarly, decomposition of CMC-coated magnetite nanoparticles started at 250 C and ended at 650 C, which
is the decomposition temperature range for NaCMC
(Figure 7). All the TGA were performed under nitrogen
atmosphere to minimize the mass increase due to iron
oxidation and allowed the polymer to decompose thermally. In both the cases, it was observed that the
percentage of weight loss is more when the magnetite
is prepared at high polymer concentration compared to

Figure 8. Temperature dependence of magnetization measured under field-cooled (FC) and zero-field-cooled (ZFC)
conditions for the samples prepared with 0.50% and 0.25%
PAA. The applied field was 0.01 T.

that formed at low polymer concentration. Again, we

know from the TEM study that the particle size is
smaller when the magnetites are prepared with high
polymer concentration. The particles with small size
have a large surface area that can adsorb a large
amount of polymer on the surface, and hence, the chance
of weight loss is greater and vice versa. Therefore, as
the particle size is increased with lowering the polymer
concentration, there is a decrease in the percentage of
weight loss.
The magnetization study was performed on the
samples prepared with 0.50% and 0.25% PAA with
mean diameter D ) 7.0 and 14.7 nm, respectively. The
magnetization measured at 0.01 T, shown in Figure 8,
exhibits the field-cooled effect. ZFC (zero-field-cooled)
curves were obtained by cooling the sample under zero
magnetic field and then measured by applying 0.01 T
in the heating cycle. FC (field-cooled) curves were
obtained like in the ZFC experiment, though samples
were cooled to the lowest temperature under 0.01 T. In
case of sample with D ) 14.7 nm, ZFC and FC curves
do not coincide up to 300 K. On the other hand, ZFC
and FC curves depart from each other below 235 K
for the sample with D ) 7.0 nm. In the case of magnetic
nanoparticles, the maximum in the ZFC curve is
characterized in general as the blocking temperature

Size-Controlled Magnetite Nanoparticles

Chem. Mater., Vol. 16, No. 18, 2004 3495

Figure 9. Magnetization curves for the samples prepared

with 0.50% and 0.25% PAA at 295 K.

(TB) of the superparamagnet, i.e., an assembly of

magnetically aligned moments in a single-domain fine
particle. A broadened peak in the ZFC curve is observed
for the case of D ) 7.0 nm, while no peak is noticed up
to 300 K for D ) 14.7 nm. If the interparticle magnetic
interaction is weak, TB can be related as KanV ) 25kBTB
for a random distribution of a single domain magnetic
particle.38 Here, V and Kan are the volume and the
anisotropy energy density constant of the particle,
respectively. Considering TB 145 K for the sample
with D ) 7.0 nm, the value of Kan is estimated to be
2.8 105 J/m3, which is close to those found in the
literature for Fe3O4 nanoparticles.39 The large anisotropy is explained by several intrinsic factors of the
nanoparticle, which mainly include magnetocrystalline,
surface, and shape anisotropy for noninteracting single
domain nanoparticles. In case of a small magnetic
particle, the interparticle interaction in general helps
to agglomerate the particles. These agglomerated nanoparticles act as a cluster, resulting in the increase of
TB. In case of the sample with D ) 14.7 nm, the
superparamagnetic blocking temperature was not observed up to 300 K, indicating the effect of such
agglomeration, which has also been observed in TEM
results.
Magnetization curves measured at 295 K, which are
shown in Figure 9, show almost immeasurable coercivity
and remanance, suggesting that these nanoparticles are
of a single domain. In case of no hysteresis, the average
size of the particle can be estimated from the initial
susceptibility, i ) (dM/dH)Hf0, coming mainly from the
largest particles. An upper limit for the magnetic size,
Dm, may be estimated using the formula40

Dm )

18kBT i
FM

(4)

where F is the density of Fe3O4 (5.18 g/cm3). The value

(38) Dorman, J. L. Revue Phys. Appl. 1981, 16, 275.
(39) Balcells, L.; Iglesias, O.; Labarta, A. Phys. Rev. B 1997, 55,
8940; Jonsson, T.; Mattsson, J.; Djurberg, C.; Khan, F. A.; Nordblad,
P.; Svedlindh, P. Phys. Rev. Lett. 1995, 75, 4138; Luo, W.; Nagel, S.
R.; Rosenbaun, T. F.; Rosensweig, R. E. Phys. Rev. Lett. 1991, 67, 2721.
(40) Carpenter, E. E. J. Magn. Magn. Mater. 2001, 225, 17.

Figure 10. Mossbauer spectra of Fe3O4 nanoparticles prepared in the presence of 0.25% and 0.50% PAA at 300 K. The
solid curves indicate the fitting of the Mossbauer spectra. The
broken curves indicate deconvoluted components of the fitting
of the Mossbauer spectrum for sample prepared with 0.25%
PAA.

of i was determined to be 34.3 10-3 and 47.5 10-3

emu/g, respectively. Using the value of saturation
magnetization, Ms, obtained from the magnetization
curve, the values of Dm were estimated to be 9 and
13 nm for the samples with D ) 7.0 and 14.7 nm,
respectively, indicating good accordance of particle sizes
estimated from magnetization and TEM experiments.
A Mossbauer study has been incorporated on the
same samples used for the magnetization studies.
Mossbauer spectra for those samples measured at 300
K are shown in Figure 10, exhibiting different features.
Only a symmetric quadrupole doublet is observed for D
) 7.0 nm. On the other hand, the spectrum for D ) 14.7
nm exhibits the superposition of a quadrupole doublet
and magnetically separated sextet, although the sextet
involves a minor contribution of R-Fe besides the
patterns expected for Fe3O4. The estimated values of
the internal magnetic fields are 47.7 ( 0.10 and 43.5 (
0.25 T, corresponding to the tetrahedral and octahedral
sites, respectively; iron ions in the spinel Fe3O4 are
distributed in two sites, and the resultant Mossbauer
spectrum is a superposition of two sextets wherein the
line from the octahedral site is broadened owing to
electron transfer between Fe2+ and Fe3+. The values of
the internal fields are 50.3 and 48.0 T at the tetrahedral
and octahedral sites, respectively, for the bulk Fe3O4
compound.41 The reduction of the internal magnetic field
with respect to the bulk counterpart is not so unlikely
for magnetic nanoparticles.42 As seen in Figure 10,
another sextet pattern corresponding to the R-Fe phase
with internal field 33.0 ( 0.3 T, which is close to the
value for bulk R-Fe,41 has also been detected for the
sample with D ) 14.7 nm. The fraction of R-Fe phase
was estimated to be 7% from the intensity, assuming
the common Debye-Waller factor. The lack of XRD
peaks corresponding to R-Fe may be due to the small
fraction of R-Fe. Moreover, the XRD peak intensities
may be decreased considerably due to line broadening.
Iron nanoparticles are strongly pyrophoric and are
(41) Greenwood, N. N.; Gibb, T. C. In Mossbauer Spectroscopy;
Chapman and Hall Ltd.: London, 1971; p 251.
(42) Giri, S.; Ganguly, S.; Bhattacharya, M. Appl. Surf. Sci. 2001,
182, 345.

3496

Chem. Mater., Vol. 16, No. 18, 2004

easily oxidized in the presence of a trace amount of

oxygen. This oxidation process starts at the surface of
the particles. In such a case, R-Fe is suggested to exist
in the core of the particle, as discussed in the literature.42,43 In case of the sample with D ) 14.7 nm, the
doublet contribution is estimated to be 12%, assuming
the common Debye-Waller factor. The quadrupole
splitting and isomer shift for the doublet are estimated
to be 0.56 ( 0.05 and 0.39 ( 0.05 mm/s, respectively,
and those for the sample with D ) 7.0 nm are 0.70 (
0.02 and 0.36 ( 0.02 mm/s, respectively. For both the
cases, the values of isomer shift are close to those found
in other Fe3O4 nanoparticles.44 The isomer shift is
typically g1.0 mm/s for Fe2+ while 0.3-0.4 mm/s for
Fe3+. The present value suggests that the average
valence is closer to Fe3+.
In the case of the nanoparticle, the magnetic anisotropy energy (E) is often close to the thermal excitation
energy, resulting in the fast fluctuation of the localized
moment. The relaxation time is given by fluc(T) ) 0
exp(E/kBT),45,46 where 0 is on the order of 10-10-10-13s
and only weakly dependent on temperature,46 and kB
is the Boltzmanns constant. This results in the relaxation of the superparamagnet in magnetic nanoparticles. In such a case, the observed magnetic feature
depends on the time scale of observation of the experiment (obs). In case of the Mossbauer study, if fluc .
obs at a particular temperature, the sextet pattern
characteristics for the ordered state is observed. When
both the time scales becomes comparable, features of
superparamagnetic relaxation start appearing initially
by reducing the splitting of the sextet pattern. The
reduction of magnetic splitting for D ) 14.7 nm with
respect to the bulk counterpart may be related to the
above feature. In the extreme case where fluc , obs at
a particular temperature, the sextet pattern turns to a
quadrupole doublet or singlet. The observation of only
a doublet pattern for D ) 7.0 nm thus indicates the
feature of superparamagnetic relaxation. On the other
hand, for D ) 14.7 nm the broad magnetic sextet
(43) Haneda, K.; Morrish, A. H. Nature 1979, 282, 186.
(44) Beach, G. S. D.; Parker, F. T.; Smith, D. J.; Crozier, P. A.;
Berkowitz, A. E. Phys. Rev. Lett. 2003, 91, 267201; Novakova, A. A.;
Lanchinskaya, V. Y.; Volkov, A. V.; Gendler, T. S.; Kiseleva, T. Y.;
Moskvina, M. A.; Zezin, S. B. J. Magn. Magn. Mater. 2003, 258, 354.
(45) Neel, L. Ann. Geophys. 1949, 5, 99.
(46) Brown, J. W. F. Phys. Rev. 1963, 130, 1677.

Si et al.

coexists with the quadrupole doublet, which is suggested

to appear due to the large distribution of particle size,
as noticed from the TEM observation (Table 1).
Conclusions
In conclusion, relatively monodisperse magnetite
nanoparticles of various sizes have been synthesized
from iron(II) ions singly in the presence of two polyelectrolytes, PAA and NaCMC. The particle size could
be varied by changing the concentration of the polyelectrolytes. From a FTIR study we were able to verify and
classify the type of attachment of the electrolyte to the
particles. The magnetization and Mossbauer studies
were performed on two samples with 0.25% and 0.50%
PAA having mean diameters 7.0 and 14.7 nm, respectively. Magnetization measurements suggest that both
of these particles are of single magnetic domain. The
superparamagnetic blocking temperature TB ) 145 K
was observed for smaller particles, while TB > 300 K
was seen for the larger particles. Mossbauer spectra at
300 K show only a quadrupole doublet for the smaller
particles, while mostly a magnetically separated sextet
is observed for the larger ones, although the latter
consists of a minor contribution from the doublet. These
results indicate that the dynamical nature of magnetization is strongly size-dependent, namely, coupled moments in the smaller particles fluctuate dynamically at
room temperature like a superparamagnet, while those
in the larger particles are mostly static, although the
dynamical component seems to be also involved in the
latter, due to the large distribution of particle size.
Acknowledgment. S.S. thanks the Council of Scientific and Industrial Research, Government of India
for providing a junior research fellowship. This work
was partially supported by the Council of Scientific and
Industrial Research, India, under Grant No. 01/(1801)/
02/EMR-II. S.G thanks JSPS, Japan for the financial
support. Thanks are also due to the Chemistry Department, Calcutta University, for allowing us to use the
TGA instrument under Department of Science and
Technology FIST Program, and to the Indian Institute
of Chemical Biology, Calcutta, for the ultracentrifuge
facility.
CM049205N